JP6769133B2 - Toner for electrostatic latent image development - Google Patents

Description

The present invention relates to a toner for electrostatic latent image development.

In recent years, electrophotographic image forming apparatus has been required to have higher speed, higher image quality, and expanded applications, and the toner for electrostatic latent image development (hereinafter, also simply referred to as "toner") used for the demand has been increased. The development of toner that can meet the demands of the market is proceeding at a rapid pace.

The demand of this market is the development of low temperature fixable toner that can be fixed with low energy from the viewpoint of high speed and energy saving. In order to meet this demand, low temperature fixability is realized by introducing a crystalline resin into the toner to lower the temperature of the thermal melting of the toner and improving the melting characteristics.

Further, in addition to low-temperature fixability, a technique for improving heat-resistant storage property is known (Patent Document 1). In this technique, an aliphatic compound is used as a monomer constituting a crystalline polyester resin, and the concentration of ester groups (carbon chain length of the monomer) in the resin is specified.

Japanese Unexamined Patent Publication No. 2014-186194

However, the technique of Patent Document 1 improves low-temperature fixability and heat-resistant storage, but when a crease is made in an image after a certain amount of time has passed after fixing, the problem that the image density of the crease becomes low, that is, so-called We found that there is a problem that the folding strength of the image deteriorates.

Therefore, an object of the present invention is to provide a toner for electrostatic latent image development capable of suppressing a decrease in folding strength of an image with time while obtaining low-temperature fixability and heat-resistant storage property.

The present inventors have conducted diligent research in order to solve the above problems. In the process, in the image formed with the toner of Patent Document 1, the affinity between the crystalline polyester resin and the main binder resin was not sufficient, and the crystalline polyester resin was compatible with the image immediately after fixing. It was found that the main binder resin and the resin quickly became incompatible with each other.

It was thought that the heat-resistant storage property (document offset resistance) of the image would be improved by the incompatible state, but in exchange for this, the folding strength of the image after a lapse of time after fixing would be deteriorated.

In the process of conducting further diligent research, the present inventors have focused on the compatibility of these resins with toners containing crystalline polyester resins and amorphous resins. Then, the crystalline polyester resin contains a structural unit derived from an aromatic carboxylic acid monomer, and the amount of the aromatic carboxylic acid monomer in the crystalline polyester resin and the amount of the aromatic compound monomer of the amorphous resin are determined. We have found that by designing these resins so that they are in an appropriate compatible state, not only low-temperature fixability and heat-resistant storage properties but also deterioration of image folding strength over time can be realized, and the present invention has been completed. I arrived.

That is, the present invention is a toner for electrostatic latent image development containing a crystalline polyester resin and an amorphous resin, wherein the crystalline polyester resin contains a structural unit derived from an aromatic carboxylic acid monomer and the aromatic. The content of the structural unit derived from the group carboxylic acid monomer is 30 to 80 mol% with respect to the structural unit derived from all the carboxylic acid monomers contained in the crystalline polyester resin, and the amorphous resin is aromatic. The content of the structural unit derived from the aromatic compound monomer, which contains the structural unit derived from the compound monomer, is 50 to 70 mol% with respect to the structural unit derived from all the monomer components contained in the amorphous resin. It is a toner for electrostatic latent image development.

According to the present invention, it is possible to provide a toner for electrostatic latent image development that can suppress a decrease in folding strength of an image with time while obtaining low temperature fixability and heat-resistant storage property.

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments. Unless otherwise specified, the operation and physical properties are measured under the conditions of room temperature (20 to 25 ° C.) / relative humidity of 40 to 50% RH. In the present specification, the black toner for static charge image development of the present invention may be simply referred to as "toner of the present invention" or "toner".

(Toner for electrostatic latent image development)
The present invention is a toner for electrostatic latent image development containing a crystalline polyester resin and an amorphous resin, wherein the crystalline polyester resin contains a structural unit derived from an aromatic carboxylic acid monomer, and the aromatic carboxylic acid is contained. The content of the structural unit derived from the acid monomer is 30 to 80 mol% with respect to the structural unit derived from all the carboxylic acid monomers contained in the crystalline polyester resin, and the amorphous resin is the aromatic compound monomer. The content of the constituent unit derived from the aromatic compound monomer, including the constituent unit derived from the resin, is 50 to 70 mol% with respect to the constituent unit derived from all the monomer components contained in the amorphous resin. It is a toner for latent image development.

As described above, in Patent Document 1, the monomer constituting the crystalline polyester resin is an aliphatic compound, and the polarity of the crystalline polyester resin and the main binder resin are determined by the ester group concentration (carbon chain length of the monomer) of the crystalline polyester. It controls the affinity with. However, in the image formed of the toner obtained in the known example, the affinity between the crystalline polyester resin and the main binder resin is not sufficient, and the crystalline polyester resin and the main binder resin that are compatible with each other in the image immediately after fixing are not sufficient. The binder resin quickly becomes incompatible with the binder resin. As a result, there is a problem that the folding strength of the image after a lapse of time has deteriorated with respect to the folding strength of the image immediately after fixing.

According to the configuration of the present invention, the aromatic compound monomer of the amorphous resin and the aliphatic carboxylic acid monomer in the crystalline polyester resin are defined in an amount that allows appropriate compatibility of these resins. It has a technical effect of suppressing a decrease in folding strength of an image over time while obtaining low-temperature fixability and heat-resistant storage property.

As described above, by using the aromatic carboxylic acid monomer as the carboxylic acid monomer constituting the crystalline polyester resin, the compatibility with the amorphous resin is improved. Further, by setting the amount of the aromatic compound monomer of the amorphous resin and the amount of the aromatic carboxylic acid monomer of the crystalline polyester resin (the amount of the aromatic ring in each resin) within the specified ranges, the image can be obtained. Both suppression of folding strength and document offset resistance can be achieved.

The mechanism that has such a technical effect is not always clear, or the phase separation between the crystalline polyester resin and the amorphous resin is achieved by the π-π interaction between the two resins that form the image after fixing. It is presumed that it can be suppressed moderately. Of course, such speculation does not limit the technical scope of the invention.

In addition, in this specification, "toner for electrostatic latent image development" may be simply referred to as "toner". Further, at least one of the crystalline polyester resin and the amorphous resin may be simply referred to as a "binding resin".

(Crystalline polyester resin)
A crystalline polyester resin usually refers to a resin obtained by a polycondensation reaction of a divalent or higher carboxylic acid (polyvalent carboxylic acid) and a divalent or higher alcohol (polyhydric alcohol) and having crystallinity. The crystalline polyester resin of the present invention contains a structural unit derived from an aromatic carboxylic acid monomer among polyvalent carboxylic acids, and the content of the structural unit derived from the aromatic carboxylic acid monomer is contained in the crystalline polyester resin. One of the characteristics is that it is 30 to 80 mol% with respect to the constituent units derived from all the carboxylic acid monomers.

Here, "having crystallinity" means having a clear melting peak in the DSC curve measured by using a differential scanning calorimeter "Diamond DSC" (manufactured by PerkinElmer). Specifically, it is measured by the method described in Examples.

The valences of the polyvalent carboxylic acid component and the polyhydric alcohol component are preferably 2 to 3 respectively, and particularly preferably 2 each.

The aromatic carboxylic acid monomer (also simply referred to as "aromatic carboxylic acid" or "aromatic polyvalent carboxylic acid") has two benzene rings or benzene rings in the unit (monomer) constituting the binder resin. It is a carboxylic acid monomer having a condensed ring. Particularly preferably, it is one benzene ring. The number of fused rings is also not particularly limited, but is usually 2 to 3.

The aromatic carboxylic acid that can be used in the crystalline polyester resin of the present invention is a concept including an acid anhydride and the like, and is preferably an aromatic dicarboxylic acid having 6 to 12 carbon atoms, for example, phthalic acid. , Telephthalic acid, isophthalic acid, t-butylisophthalic acid, orthophthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-phenylene diacetic acid, diphenyl-p, p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid. Acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracendicarboxylic acid, 4,4'-biphenyldicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, Examples thereof include pyrentricarboxylic acid and pyrenetetracarboxylic acid. Among these, it is preferable to use terephthalic acid, isophthalic acid, orthophthalic acid, and p-phenylene diacetic acid from the viewpoint of compatibility with the amorphous resin.

As an aliphatic polyvalent carboxylic acid monomer (also simply referred to as "aliphatic carboxylic acid" or "aliphatic polyvalent carboxylic acid") that can be used in the crystalline polyester resin of the present invention and can be used together with the above aromatic carboxylic acid. For example, oxalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, β-methyladipic acid, pimelliic acid, suberic acid, mesaconic acid, azelaic acid, citraconic acid, sebacic acid, 1 , 9-Nonandicarboxylic acid, 1,10-decandicarboxylic acid (dodecanedioic acid), 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecane Examples thereof include dicarboxylic acid, 1,16-hexadecanedicarboxylic acid and 1,18-octadecanedicarboxylic acid. Among these, from the viewpoint of increasing the degree of crystallization, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonandicarboxylic acid, 1,10-decandicarboxylic acid (dodecanedioic acid), 1 , 11-Undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid are preferably used.

As the aliphatic carboxylic acid, it is preferable to use a linear type. There is an advantage that the crystallinity is improved by using the linear type. The aliphatic carboxylic acid is preferably an aliphatic dicarboxylic acid having 6 to 14 carbon atoms.

As described above, in the present invention, the content of the structural unit derived from the aromatic carboxylic acid monomer is 30 to 80 mol% with respect to the structural unit derived from all the carboxylic acid monomers contained in the crystalline polyester resin. .. If it is too small, the compatibility with the amorphous resin is too low, and the folding strength of the image changes with time. If it is too much, the compatibility is too high, and the document offset resistance deteriorates.

According to a preferred embodiment of the present invention, the content of the structural unit derived from the aromatic carboxylic acid monomer is 40 to 70 mol% with respect to the structural unit derived from all the carboxylic acid monomers contained in the crystalline polyester resin. is there. According to such a form, the intended technical effect of the present invention can be efficiently achieved. Further, according to a preferred embodiment of the present invention, the content of the structural unit derived from the aromatic carboxylic acid monomer is 42 to 60 mol with respect to the structural unit derived from all the carboxylic acid monomers contained in the crystalline polyester resin. %, Which is 45-55 mol%. According to this form, the desired effect can be obtained in a well-balanced manner.

Further, as the polyhydric alcohol component that can be used in the crystalline polyester resin of the present invention, it is preferable to use an aliphatic polyhydric alcohol, and it is preferable to use a linear type. There is an advantage that the crystallinity is improved by using the linear type.

Examples of the aliphatic polyhydric alcohol include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. 1,7-Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, Examples thereof include 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol, neopentyl glycol, cyclohexanediol and the like. Among these, from the viewpoint of increasing the degree of crystallization, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1, It is preferable to use 9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, and 1,14-tetradecanediol.

The aliphatic polyhydric alcohol is preferably an aliphatic diol having 4 to 14 carbon atoms.

The aliphatic polyhydric alcohol that can be used in the crystalline polyester resin of the present invention may be used in combination with an aromatic polyhydric alcohol as long as it does not inhibit crystallization, and specific examples will be described later. An aromatic polyhydric alcohol that can be used for the amorphous polyester resin may be appropriately selected.

The composition mol% of the polyvalent carboxylic acid component for forming the crystalline polyester resin and the polyhydric alcohol component is preferably 100 composition mol% in total.

The melting point of the crystalline polyester resin is preferably 65 to 95 ° C, more preferably 70 to 93 ° C. When the melting point of the crystalline polyester resin is in the above range, sufficient low-temperature fixability can be obtained. The melting point of the crystalline polyester resin can be controlled by the resin composition. The melting point is measured by the method described in Examples.

The weight average molecular weight (Mw) of the crystalline polyester resin is preferably 5,000 to 100,000, more preferably 10,000 to 80,000, and more preferably 15,000 to 30,000. Especially preferable. The weight average molecular weight is measured by the method described in Examples.

The method for producing the crystalline polyester resin is not particularly limited, and for example, it can be produced by polycondensing (esterifying) the polyvalent carboxylic acid and the polyhydric alcohol using a known esterification catalyst. it can.

As catalysts that can be used in the production of crystalline polyester resins, alkali metal compounds such as sodium and lithium; compounds containing Group 2 elements such as magnesium and calcium; aluminum, zinc, manganese, antimony, titanium, tin, Examples thereof include metal compounds such as zirconium and germanium; phosphite compounds; phosphoric acid compounds; and amine compounds. Specifically, examples of the tin compound include dibutyltin oxide (dibutyltin oxide), tin octylate, tin dioctylate, and salts thereof. Titanium compounds include titanium alkoxides such as tetranormal butyl titanate (Ti (OBu) ₄ ), tetraisopropyl titanate, tetramethyl titanate, and tetrastearyl titanate; titanium acylates such as polyhydroxytitanium stearate; titanium tetraacetylacetonate, Examples thereof include titanium chelates such as titanium lactate and titanium triethanol aminated. Examples of the germanium compound include germanium dioxide and the like. Further, examples of the aluminum compound include oxides such as polyaluminum hydroxide, aluminum alkoxide, and tributylaluminate. These may be used individually by 1 type or in combination of 2 or more type.

The polymerization temperature is not particularly limited, and can be appropriately adjusted in order to obtain the desired product, and is preferably 70 to 250 ° C. The polymerization time is not particularly limited, but is preferably 0.5 to 12 hours. Further, the polymerization temperature may be gradually raised to 10 to 50 ° C., and the inside of the reaction system may be depressurized as necessary. Further, the reaction may be continued after cooling.

(Amorphous resin)
According to the present invention, the amorphous resin contains a structural unit derived from an aromatic compound monomer, and the content of the structural unit derived from the aromatic compound monomer is derived from all the monomer components contained in the amorphous resin. One of the features is that it is 50 to 70 mol% with respect to the constituent unit of.

Here, the amorphous resin is a resin that does not have a melting point and has a relatively high glass transition temperature (Tg) when differential scanning calorimetry (DSC) is performed. The glass transition temperature is preferably 40 to 70 ° C, preferably 40 to 60 ° C. The molecular weight of the amorphous resin is preferably 2,000 to 100,000, preferably 20,000 to 50,000 in terms of weight average molecular weight (Mw).

Further, the aromatic compound monomer has a benzene ring or a ring obtained by condensing two or more benzene rings among the units (monomers) constituting the binder resin. Particularly preferably, it is one benzene ring. The number of fused rings is also not particularly limited, but is usually 2 to 3.

As described above, the content of the structural unit derived from the aromatic compound monomer is 50 to 70 mol% with respect to the structural unit derived from all the monomer components contained in the amorphous resin. If it is too small, the compatibility with the crystalline polyester resin is too low, and the folding strength of the image changes with time. If it is excessive, the compatibility is improved too much, and the document offset resistance deteriorates.

Further, in order to efficiently exert the desired technical effect of the present invention, according to the preferred embodiment of the present invention, the content of the structural unit derived from the aromatic compound monomer is contained in the amorphous resin. It is 52 to 68 mol%, more preferably 55 to 65 mol%, based on the constituent units derived from all the monomer components. Within such a range, the desired effect of the present invention can be obtained in a well-balanced manner.

(Amorphous polyester resin)
According to a preferred embodiment of the present invention, the amorphous resin contains a polyester resin. Such a form has a technical effect of improving fixability.

Amorphous polyester resin usually refers to a resin having amorphousness obtained by a polycondensation reaction of a divalent or higher carboxylic acid (polyvalent carboxylic acid) and a divalent or higher alcohol (polyhydric alcohol). ..

Specific examples of the aromatic carboxylic acid that can be used for the amorphous polyester resin are not particularly limited, and may be appropriately selected from the aromatic carboxylic acids listed above.

The specific example of the aliphatic carboxylic acid that can be used together with the aromatic carboxylic acid is not particularly limited, and may be appropriately selected from the aliphatic carboxylic acids listed above.

Aromatic polyhydric alcohols that can be used in amorphous polyester resins include dihydric alcohols such as bisphenol A ethylene oxide adduct and bisphenol A propylene oxide adduct; glycerin, pentaerythritol, hexamethylol melamine, and hexa. Examples thereof include trivalent or higher valent polyols such as ethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine. These may be used alone or in combination of two or more.

The aliphatic polyhydric alcohol that can be used together with the aromatic polyhydric alcohol may be appropriately selected from, for example, the aliphatic polyhydric alcohols listed above.

The method for producing the amorphous polyester resin is not particularly limited, and for example, the description of the method for producing the crystalline polyester resin can be similarly applied.

(Vinyl resin)
According to a preferred embodiment of the present invention, the amorphous resin contains a vinyl resin from the viewpoint of environmental stability of charging.

The vinyl resin is not particularly limited as long as it is a polymer of a vinyl compound, and examples thereof include an acrylic acid ester resin, a styrene acrylic copolymer, and an ethylene / vinyl acetate resin. One of these may be used alone, or two or more thereof may be used in combination. Among the above vinyl resins, considering the manufacturability in the emulsion aggregation method (that is, a toner having a sharp particle size distribution can be obtained by producing a latex having uniform aggregation) and the plasticity at the time of heat fixing. , Styrene-acrylic copolymer is preferable.

(Styrene acrylic copolymer)
The styrene-acrylic copolymer is preferably formed by carrying out polymerization using at least a styrene monomer and a (meth) acrylic acid ester monomer. Here, the styrene monomer includes not only styrene represented by the structural formula of CH ₂ = CH-C ₆ H ₅ but also a structure having a known side chain or functional group in the styrene structure. Is.

Further, the (meth) acrylic acid ester monomer has a functional group having an ester bond in the side chain. _{Specifically,} CH 2 = CHCOOR (R is an alkyl group) other acrylic acid ester monomer represented _by, methacrylic acid ester represented by _{CH 2 = C (CH 3)} COOR (R is an alkyl group) A vinyl ester compound such as a monomer is included.

Specific examples of the styrene monomer and the (meth) acrylic acid ester monomer capable of forming the styrene-acrylic copolymer are shown below, but the present invention is not limited to those shown below.

Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, and p-. Examples thereof include tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene and pn-dodecyl styrene.

Further, the (meth) acrylic acid ester monomer is typically the acrylic acid ester monomer and the methacrylate ester monomer shown below, and examples of the acrylic acid ester monomer include methyl acrylate. Examples thereof include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate and phenyl acrylate phenyl. Examples of the methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate. , Lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate and the like.

These styrene monomers and (meth) acrylic acid ester monomers can be used alone or in combination of two or more.

In addition to the above-mentioned copolymers formed only of the styrene monomer and the (meth) acrylic acid ester monomer, the styrene-acrylic copolymer also includes these styrene monomer and the (meth) acrylic acid ester. In addition to the monomer, some are formed by using a general vinyl monomer in combination. Hereinafter, the vinyl monomer that can be used in combination when forming the styrene-acrylic copolymer according to the present invention is preferably a vinyl monomer having a carboxy group. Specific examples of the vinyl monomer having a carboxy group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, silicic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester and the like. ..

The method for forming the vinyl resin is not particularly limited, and examples thereof include a method of polymerizing a monomer using a known oil-soluble or water-soluble polymerization initiator.

Examples thereof include a method of polymerizing a monomer using a known oil-soluble or water-soluble polymerization initiator. Specific examples of the oil-soluble polymerization initiator include the following azo-based or diazo-based polymerization initiators and peroxide-based polymerization initiators.

Examples of the azo or diazo polymerization initiator include 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, and 1,1'-azobis (cyclohexane-1). -Carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like.

Examples of the peroxide-based polymerization initiator include benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2, Examples thereof include 4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis- (4,5-t-butylperoxycyclohexyl) propane, tris- (t-butylperoxy) triazine and the like.

Further, when resin particles are formed by the emulsion polymerization method, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate (potassium persulfate) and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, and hydrogen peroxide.

If necessary, a known chain transfer agent such as n-octyl mercaptan may be used.

(Mass ratio of crystalline polyester resin and amorphous resin)
According to a preferred embodiment of the present invention, the mass ratio of the amorphous resin to the crystalline polyester resin is 3 to 50. According to a more preferred embodiment of the present invention, the mass ratio of the amorphous resin to the crystalline polyester resin is 4 to 19. In particular, when it is 4 or more, the amount of the crystalline polyester resin becomes appropriate with respect to the amorphous resin, and the crystalline polyester resin and the amorphous resin in the image after fixing are in a compatible state. By suppressing it, in particular, when it is 19 or less, the amount of the crystalline polyester resin becomes an appropriate amount with respect to the amorphous resin, and the crystalline polyester resin and the amorphous resin in the image after fixing are in a phase-separated state. Suppress that. More preferably, it is 6 to 15, and in the case of such a form, such a technical effect is more exhibited.

(toner)
The toner of the preferred embodiment of the present invention is obtained by adding an external additive to toner matrix particles containing a crystalline polyester resin and an amorphous resin, and a colorant and, if necessary, an internal additive. The toner of the present invention may have a single-layer structure or a core-shell structure. Conventionally known knowledge is appropriately applied to the method for manufacturing the core-shell structure.

(Colorant)
As the colorant, a known colorant can be used.

Specifically, examples of the colorant contained in the yellow toner include C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, C.I. I. Pigment Yellow 14, 17, 74, 93, 94, 138, 155, 180, 185 and the like. These can be used alone or in combination of two or more. Among these, especially C.I. I. Pigment Yellow 74 is preferred. The content of the colorant contained in the yellow toner is preferably 1 to 10 parts by mass, and more preferably 2 to 8 parts by mass with respect to 100 parts by mass of the binder resin.

Specifically, examples of the colorant contained in the magenta toner include C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 122, C.I. I. Pigment Red 5, 48: 1, 53: 1, 57: 1, 122, 139, 144, 149, 166, 177, 178, 222 and the like. These can be used alone or in combination of two or more. Among these, especially C.I. I. Pigment Red 122 is preferred. The content of the colorant contained in the magenta toner is preferably 1.00 to 7.00 parts by mass, and more preferably 1.52 to 4.16 parts by mass with respect to 100 parts by mass of the binder resin. Is.

Specifically, examples of the colorant contained in the cyan toner include C.I. I. Pigment Blue 15: 3 and the like. The content of the colorant contained in the cyan toner is preferably 1 to 20 parts by mass, and more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the binder resin.

Examples of the colorant contained in the black toner include carbon black and titanium black. Examples of carbon black include channel black, furnace black, acetylene black, thermal black, and lamp black. The content of the colorant contained in the black toner is preferably 5 to 15 parts by mass, and more preferably 6 to 12 parts by mass with respect to 100 parts by mass of the binder resin.

(Internal additive)
The internal additive is not particularly limited, and examples thereof include a charge control agent and a release agent.

(Charge control agent)
The charge control agent is not particularly limited as long as it is a substance capable of giving positive or negative charge by triboelectric charging, and various known positive charge control agents and negative charge control agents can be used.

The content of the charge control agent is preferably 0.01 to 30 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

(Release agent)
As the release agent, various known waxes can be used.

Examples of the wax include polyolefin waxes such as polyethylene wax and polypropylene wax, branched chain hydrocarbon waxes such as microcrysterin wax, long chain hydrocarbon waxes such as paraffin wax and sazole wax, and dialkyls such as distearyl ketone. Ketone wax, carnauba wax, montan wax, behenyl behenate, trimethylpropantribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecanediol di Examples thereof include ester waxes such as stearate, tristearyl trimellitic acid and distealyl maleate, and amide waxes such as ethylenediaminebehenylamide and tristealylamide trimellitic acid.

The content of the release agent is preferably 5 to 30 parts by mass, more preferably 6 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

(Average circularity of toner matrix particles)
Toner matrix particles can be produced by an emulsion aggregation method. Therefore, the shape of the produced toner matrix particles (toner) becomes close to a true sphere. The average circularity (simply also referred to as circularity) of the toner matrix particles represented by the following formula 1 is preferably 0.910 or more. Further, from the viewpoint of improving transfer efficiency and charging stability, it is more preferably 0.920 to 0.996.

The average circularity is measured by the method described in Examples.

(Diameter of toner matrix particles)
The particle size of the toner matrix particles is preferably 3 to 8 μm in terms of volume-based median diameter (D50). This particle size can be controlled by the concentration of the flocculant, the fusion time, and the composition of the polymer itself. When the volume-based median diameter (D50) is 3 to 8 μm, reproducibility of fine lines and high image quality of photographic images can be achieved. The volume-based median diameter (D50) can be measured by, for example, "Multisizer 3" (manufactured by Beckman Coulter).

(External agent)
An external additive may be added to the toner matrix particles for the purpose of improving fluidity and chargeability. Examples of the external additive include inorganic oxide particles such as silica particles, alumina particles, and titanium oxide particles having a number average primary particle diameter of 5 to 30 nm, and inorganic titanium acids such as strontium titanate and zinc titanate. Examples include inorganic particles such as compound particles.

From the viewpoint of heat-resistant storage and environmental stability, the surface may be hydrophobized with a known surface treatment agent such as a coupling agent, and the surface treatment agent is particularly preferably dimethyldimethoxysilane or hexamethyl. Examples thereof include disilazan (HMDS), methyltrimethoxysilane, isobutyltrimethoxysilane, and decyltrimethoxysilane. The degree of hydrophobization is preferably about 30 to 90.

(Toner manufacturing method)
Next, the method for producing the toner of the present invention will be described. The method for producing the toner of the present invention is preferably an emulsion aggregation method. By adopting the emulsification / aggregation method, there is an advantage that the particle size of the toner can be reduced and the generation of fine powder components can be suppressed, so that a toner having a sharp particle size distribution can be obtained. It also has the advantage of requiring less energy during manufacturing.

According to a preferred embodiment of the present invention, the emulsion aggregation method is a toner such as a dispersion liquid of crystalline polyester resin fine particles, a dispersion liquid of amorphous resin fine particles, a dispersion liquid of colorant fine particles, and a dispersion liquid of a release agent. The dispersions of the components constituting the parent particles are mixed in an aqueous environment, these are aggregated by adding a flocculant, and if necessary, a coagulation terminator is added to control the particle size, and fusion is performed. This is a method of controlling the shape, thereby producing toner matrix particles.

In any of the above dispersions, for dispersion in advance, an anionic surfactant such as a known surfactant (for example, polyoxyethylene (2) sodium lauryl ether sulfate, sodium lauryl sulfate (sodium dodecyl sulfate)) is used. Surfactant) may be used.

Further, after mixing these dispersions, the pH may be adjusted to about 8 to 11 with a known pH adjuster (for example, sodium hydroxide).

Next, the crystalline polyester resin fine particles, the amorphous resin fine particles, the release agent, and the colorant fine particles are aggregated in an aqueous medium, and these particles are fused to prepare toner base particles. At this time, these may be aggregated together, or they may be aggregated in any order.

In a preferred form, an alkali metal salt or an alkali metal salt or an alkali metal salt or an alkali metal salt or a mixture of a dispersion of crystalline polyester resin fine particles, a dispersion of amorphous resin fine particles, a release agent dispersion, and a colorant fine particle dispersion is used. Alkaline earth (Group 2) metal salts and the like are added as coagulants to promote fusion. At this time, it is preferable to add the flocculant over 5 to 20 minutes while keeping the temperature at 25 to 35 ° C., and raise the temperature to about 70 to 90 ° C. over 30 to 90 minutes to grow the particles. Then, when the size of the toner matrix particles reaches the target size, an aggregation terminator is added to stop the aggregation.

Then, the reaction system is heat-treated to mature the toner matrix particles until they have a desired shape (progressing fusion) to complete the toner matrix particles. As the aging treatment, the liquid temperature is set to 70 to 90 ° C., heating and stirring are performed for 0.5 to 6 hours, and the average circularity of the particles is usually 0.91 or more, preferably 0.920 to 0.996. Proceed with fusion. Further, it is preferable to perform cooling at an arbitrary speed after the fusion has proceeded.

In the aging step, by applying shear by heat and stirring to the toner particles, it is possible to fuse the resin fine particles in the aggregated particles and control the circularity and surface properties of the particles.

Finally, the toner matrix particles can be produced by cooling to a desired temperature at a desired cooling rate and performing solid-liquid separation, washing, and drying a desired number of times.

(Coagulant)
The flocculant that promotes aggregation is not particularly limited, but one that is selected from metal salts is preferable as one that grows particles by using a charge neutralization reaction and a cross-linking action. Metal salts include monovalent metal salts such as alkali metal salts such as sodium, potassium and lithium; divalent metal salts such as calcium, magnesium, manganese and copper; trivalent metal salts such as iron and aluminum. And so on.

Specific examples of the metal salt include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate, aluminum sulfate, polyaluminum chloride, zinc acetate and the like. Among these, it is particularly preferable to use a divalent metal salt because aggregation can be promoted with a smaller amount. These can be used alone or in combination of two or more.

(Coagulation terminator)
As the aggregation terminator that stops the growth of aggregated particles, a salt that relaxes the aggregation action is used. For example, sodium chloride, polyhydric organic acids or salts thereof, amino acids, polyphosphonic acids or salts thereof can be used. A method of alleviating the agglutination action by changing the pH in the system can also be used.

(Addition of external additive)
Toners can be prepared by producing toner matrix particles as described above and adding the above-mentioned external additives by a known method (for example, mixing with a Henschel mixer or the like). At this time, the peripheral speed of the rotary blade is preferably about 20 to 60 m / sec, the temperature is preferably about 25 to 45 ° C., and the time is preferably about 10 to 30 minutes. If necessary, coarse particles may be removed.

(Developer)
For example, the toner of the present invention may contain a magnetic substance and be used as a one-component magnetic toner, may be mixed with a so-called carrier and used as a two-component developer, or a non-magnetic toner may be used alone. , Any of which can be preferably used.

As the carrier constituting the two-component developer, magnetic particles made of metals such as iron, ferrite and magnetite, and conventionally known materials such as alloys of these metals with metals such as aluminum and lead can be used, in particular. It is preferable to use ferrite particles.

The carrier preferably has a volume average particle diameter of 15 to 100 μm, and more preferably 25 to 60 μm.

As the carrier, it is preferable to use a carrier coated with a resin or a so-called resin-dispersed carrier in which magnetic particles are dispersed in the resin. The resin composition for coating is not particularly limited, and for example, an olefin resin, a cyclohexyl methacrylate-methyl methacrylate copolymer, a styrene resin, a styrene acrylic resin, a silicone resin, a polyester resin, a fluorine resin, or the like is used. Further, the resin for forming the resin dispersion type carrier is not particularly limited, and known ones can be used. For example, acrylic resin, styrene acrylic resin, polyester resin, fluororesin, phenol resin and the like can be used. Can be done.

Hereinafter, typical embodiments of the present invention will be shown and the present invention will be further described, but of course, the present invention is not limited to these embodiments. Unless otherwise specified in the examples, "parts" represents "parts by mass" and "%" represents "% by mass".

[Measuring method]
(Molecular weight)
In the present invention, the molecular weight by gel permeation chromatography (GPC) is a value measured as follows.

Specifically, using the apparatus "HLC-8120GPC" (manufactured by Toso Co., Ltd.) and the column "TSKguardsample + TSKgelSuperHZ-M3 series" (manufactured by Toso Co., Ltd.), the carrier solvent was flown at a flow rate of 0.2 ml / while maintaining the column temperature at 40 ° C. Flow at min and treat the measurement sample at room temperature for 5 minutes using an ultrasonic disperser. Dissolve in a carrier solvent to a concentration of 1 mg / ml under dissolution conditions, and then treat with a membrane filter with a pore size of 0.2 μm. To obtain a sample solution, 10 μL of this sample solution was injected into the apparatus together with the above carrier solvent, detected using a refractive index detector (RI detector), and the molecular weight distribution of the measurement sample was measured as monodisperse polystyrene standard particles. It is calculated using the calibration line measured using. Ten points were used as polystyrene for calibration curve measurement.

Chloroform was used as the carrier solvent when measuring the crystalline polyester. Tetrahydrofuran (THF) was used as the carrier solvent when measuring the amorphous resin.

The results are shown in Tables 3, 5 and 7.

(Melting point)
The melting point of the crystalline polyester resin is a value measured as follows.

The melting point of crystalline polyester indicates the temperature of the peak top of a clear melting peak and is measured by DSC by differential scanning calorimetry using "Diamond DSC" (manufactured by PerkinElmer).

Here, the clear melting peak is specifically a peak in which the half width of the melting peak is within 15 ° C. when measured at a heating rate of 10 ° C./min in differential scanning calorimetry (DSC). Means that.

Specifically, 1.0 mg of a measurement sample (crystalline polyester resin) is sealed in an aluminum pan (KITNO.B0143013), set in a sample holder of "Diamond DSC", and measured at a measurement temperature of 0 to 200 ° C. The temperature of heating-cooling-heating is controlled under the measurement conditions of a heating rate of 10 ° C./min and a temperature-decreasing rate of 10 ° C./min, and the analysis is performed based on the data of the second heating.

The results are shown in Table 3.

<Toner 1>
[Synthetic example of crystalline polyester resin [cpr1]]
Nitrogen inlet tube, a dehydration tube, put Ti (OBu) 4 _0.4 parts by four-necked flask equipped with a stirring拌器and a thermocouple as the raw material monomer and esterification catalyst polycondensation resin below, 180 ° C. Was reacted for 4 hours (Table 2).

・ 190 parts by mass of sebacic acid (decanedioic acid) ・ 230 parts by mass of terephthalic acid ・ 280 parts by mass of 1,6-hexanediol After that, the temperature is raised to 210 ° C at 10 ° C per hour, held at 210 ° C for 5 hours, and then depressurized. A crystalline polyester resin [cpr1] was obtained by reacting under (8 kPa) for 1 hour. The obtained crystalline polyester resin [cpr1] had a number average molecular weight (Mw) of 18,000 and a melting point of 91 ° C.

[Preparation Example of Aqueous Dispersion Liquid [cpd1] of Crystalline Polyester Resin Fine Particles]
30 parts by mass of the crystalline polyester resin [cpr1] was melted and transferred to the emulsification disperser "Cavitron CD1010" (manufactured by Eurotec Limited) at a transfer rate of 100 parts by mass per minute. Further, at the same time as the transfer of the crystalline polyester resin [cpr1] in the molten state, 70 parts by mass of the reagent ammonia water was diluted with ion-exchanged water in the aqueous solvent tank with respect to the emulsification disperser, and the concentration was 0.37% by mass. Dilute aqueous ammonia was transferred at a transfer rate of 0.1 liters per minute while heating to 100 ° C. with a heat exchanger. Then, by operating this emulsifying disperser under the conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ² , an aqueous dispersion liquid [cpd1] of crystalline polyester resin fine particles having a volume-based median diameter of 200 nm is prepared. did.

[Synthetic example of amorphous polyester resin [apr1]]
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 1.0 part by mass of Ti (OBu) ₄ as a raw material monomer and an esterification catalyst of the following polycondensation resin was placed at 180 ° C. Was reacted for 4 hours.

・ 132 parts by mass of fumaric acid ・ 45 parts by mass of terephthalic acid ・ 500 parts by mass of bisphenol A propylene oxide 2 mol adduct Then, the temperature was raised to 210 ° C. at 10 ° C. per hour, held at 210 ° C. for 5 hours, and then reduced under reduced pressure (8 kPa). ) Was reacted for 1 hour.

Next, after cooling to 200 ° C., the reaction was carried out under reduced pressure (20 kPa) for 1 hour to obtain an amorphous polyester resin [apr1]. The obtained amorphous polyester resin [apr1] had a weight average molecular weight (Mw) of 35,000.

[Preparation Example of Aqueous Dispersion Liquid [apd1] of Amorphous Polyester Resin Fine Particles]
30 parts by mass of the crystalline polyester resin [apr1] was melted and transferred to the emulsification disperser "Cavitron CD1010" (manufactured by Eurotec Limited) at a transfer rate of 100 parts by mass per minute. Further, at the same time as the transfer of the melted amorphous polyester resin [apr1], 70 parts by mass of the reagent ammonia water was diluted with ion-exchanged water in the aqueous solvent tank for the emulsification disperser, and the concentration was 0.37 mass. % Dilute aqueous ammonia was transferred at a transfer rate of 0.1 liters per minute while heating to 100 ° C. with a heat exchanger. Then, by operating this emulsifying disperser under the conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ² , a volume-based median diameter of 180 nm, an aqueous dispersion of amorphous polyester resin fine particles [appd1] can be obtained. Prepared.

[Preparation example of aqueous dispersion [avd1] of amorphous resin (vinyl resin) fine particles [avr1]]
8 parts by mass of sodium dodecyl sulfate and 2733 parts by mass of ion-exchanged water are charged in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introduction device, and the internal temperature is adjusted while stirring at a stirring rate of 230 rpm under a nitrogen stream. The temperature was raised to 80 ° C. After raising the temperature, 10 parts by mass of potassium persulfate dissolved in 200 parts by mass of ion-exchanged water was added, and the liquid temperature was adjusted to 80 ° C. again.
・ 477 parts by mass of styrene ・ 123 parts by mass of methyl methacrylate ・ 180 parts by mass of n-butyl acrylate ・ 35 parts by mass of methacrylic acid ・ 8 parts by mass of n-octyl mercaptan After dropping a monomer mixture consisting of 8 parts by mass over 1 hour, 80 parts After polymerization was carried out by heating and stirring at ° C. for 2 hours, the mixture was cooled to 20 ° C. to prepare an aqueous dispersion of amorphous resin fine particles made of vinyl resin.

Regarding the obtained aqueous dispersion of amorphous resin fine particles, the volume-based median diameter of the amorphous resin fine particles was 150 nm, the glass transition point (Tg) was 53 ° C., and the weight average molecular weight (Mw) was 32,000. It was.

[Example of preparation of release agent dispersion]
-Paraffin wax (HNP0190, manufactured by Nippon Seiwa Co., Ltd. (melting point 85 ° C)) 200 parts by mass-Sodium dodecyl sulfate 20 parts by mass-Ion-exchanged water 2200 parts by mass A solution containing the above components is heated to 95 ° C. After sufficiently dispersing with Ultratarax T50 manufactured by IKA, dispersion treatment was carried out with a pressure discharge type paraffin homogenizer to prepare a release agent dispersion solution [w1] having a volume-based median diameter of 100 nm.

[Preparation example of aqueous dispersion [Bk] of colorant fine particles]
90 parts by mass of sodium dodecyl sulfate was added to 1600 parts by mass of ion-exchanged water. While stirring this solution, 420 parts by mass of carbon black "Legal 330R" (manufactured by Cabot) was gradually added, and then dispersion treatment was performed using a stirrer "Clearmix" (manufactured by M-Technique). , An aqueous dispersion [Bk] of the colorant fine particles was prepared.

With respect to the obtained aqueous dispersion [Bk] of the colorant fine particles, the average particle size (volume-based median diameter) of the colorant fine particles was 110 nm.

[Example 1: Production example 1 of black toner]
In a reaction vessel equipped with a stirrer, temperature sensor, and cooling tube,
-Amorphous resin fine particle aqueous dispersion [appd1] 540 parts by mass (solid content equivalent),
-Aqueous dispersion of crystalline polyester resin fine particles [cpd1] 60 parts by mass (solid content equivalent),
-Release agent dispersion [w1] 60 parts by mass (solid content equivalent),
-Aqueous dispersion of colorant fine particles [Bk1] 48 parts by mass (solid content equivalent)
Was added, and a 5 mol / liter aqueous sodium hydroxide solution was added to adjust the pH to 10.

Next, an aqueous solution prepared by dissolving 50 parts by mass of magnesium chloride in 50 parts by mass of ion-exchanged water was added under stirring at 30 ° C. over 10 minutes. The temperature rise is started, the temperature of this system is raised to 80 ° C. over 60 minutes, the particle size of the associated particles is measured with "Colter Multisizer 3" (manufactured by Beckman Coulter), and the volume-based median diameter is determined. The stirring speed was controlled so as to be 6.0 μm. Then, an aqueous solution prepared by dissolving 190 parts by mass of sodium chloride in 760 parts by mass of ion-exchanged water was added to stop particle growth.

Further, the particles were fused by heating and stirring at 80 ° C. for 3 hours, and then cooled to 30 ° C. at a cooling rate of 1 ° C./min. The obtained toner matrix particles were measured using a measuring device "FPIA-3000" (manufactured by Sysmex Corporation) (the number of HPFs detected was 4000), and the average circularity was 0.957.

Next, the operation of solid-liquid separation, redispersion of the dehydrated toner cake in ion-exchanged water, and solid-liquid separation was repeated three times for washing, and then dried at 40 ° C. for 24 hours to obtain black toner matrix particles [1X]. Got The size of the black toner matrix particles [1X] was 6.0 μm in median diameter (D50). The particle size was the same in all the examples and comparative examples.

In 100 parts by mass of the obtained black toner base particles [1X], 0.6 parts by mass of hydrophobic silica (number average primary particle diameter = 12 nm, degree of hydrophobicity = 68) and hydrophobic titanium oxide (number average primary particle diameter =). 20 nm, degree of hydrophobization = 63) 1.0 part by mass is added and mixed with a "Henshell mixer" (manufactured by Mitsui Miike Kakoki Co., Ltd.) at a peripheral speed of 35 m / sec and 32 ° C for 20 minutes. After that, coarse particles were removed using a sieve having a mesh size of 45 μm to obtain a toner [1].

A ferrite carrier having a volume average particle diameter of 30 μm coated with a copolymer resin of cyclohexyl methacrylate and methyl methacrylate (monomer mass ratio = 1: 1) was used with respect to the toner [1] so that the toner concentration was 6% by mass. The developer [1] was obtained by mixing the mixture.

<Toner 2-22>
The toners 2 to 22 were produced in the same manner as the toner 1 by changing the composition so as to have the composition shown in Table 1 below.

A summary of toners 1 to 22 is shown in Table 1.

[Evaluation]
(Evaluation of image folding strength)
Using the copying machine "bizhub PRESS (registered trademark) C1070" (manufactured by Konica Minolta), the fixing device was modified so that the surface temperature (fixing temperature) of the heating roller could be changed in the range of 120 to 200 ° C. Each of them was loaded with a developer and used.

Fixing a solid image with a toner adhesion of 11 g / m ² on A4 size high-quality paper "CF paper" (manufactured by Konica Minolta) in an environment of normal temperature and humidity (temperature 20 ° C, humidity 50% RH) The experiment was repeated up to 200 ° C., changing the set fixing temperature from 120 ° C. in increments of 2 ° C.

The reflection density of black was measured at 9 points on the printed matter at each fixing temperature obtained above, and the average value was taken as [D1]. The reflection density of black was measured using a spectrophotometer "Gretag Macbeth Spectrolino" (manufactured by Gretag Macbeth). The measurement was carried out under the conditions that a D65 light source was used as the light source, a φ4 mm aperture was used for the reflection measurement aperture, the measurement wavelength range was 380 to 730 nm at 10 nm intervals, the viewing angle (observer) was 2 °, and a dedicated white tile was used for reference adjustment. did.

Then, a solid image was quickly creases by applying a load of 300 kPa with a folding machine, and compressed air of 0.35 MPa was discharged from a nozzle having a diameter of 2 mm from a distance of 1 cm from the image and sprayed into the creases of the image.

The reflection density of black was measured at 9 points in the portion where the compressed air was blown, and the average value was taken as [D2].

[D2] / [D1] were calculated for the printed matter at each fixing temperature, and the temperature exceeding 0.9 for the first time was defined as the pass temperature [T1] for the folding strength.

Those having [T1] of 150 ° C. or lower were judged to be acceptable.

(Evaluation of changes in image folding strength over time)
The printed matter fixed at the temperature [T1] obtained by evaluating the folding strength of the image was allowed to stand in an environment of normal temperature and humidity (temperature 20 ° C., humidity 50% RH) for 1 month, and then the creases of the printed matter were folded. After making a crease in the same manner as above for the part without the mark, compressed air was blown. The reflection density of black was measured at 9 points in the portion where the compressed air was blown, and the average value was taken as [D3].
Using [D1] to [D3] obtained above, the value of the following formula was calculated.

([D3] / [D1])-([D2] / [D1])
-Evaluation criteria-
Those having the above values less than 0.10 were regarded as acceptable, and those having the above values of 0.10 or more were judged to have a large change in image intensity with time and were rejected.

(Evaluation of document offset resistance)
A4 size coated paper "POD Gloss Coat 100" (A4 size coated paper "POD Gloss Coat 100" (manufactured by Konica Minolta) using a copying machine "bizhub PRESS (registered trademark) C1070" in an environment of normal temperature and humidity (temperature 20 ° C., humidity 50% RH). A solid image with a toner adhesion amount of 9 g / m ² was output on the Oji Paper Co., Ltd.). A blank sheet of POD gloss coat 100 was placed on the obtained printed matter, a load equivalent to 10 g / cm ² was applied thereto, and the printed matter was left in an environment of a temperature of 50 ° C. and a humidity of 40% RH for 3 days, and then piled up. The printed matter was peeled off, and the image defect was evaluated according to the following evaluation criteria.

In the present invention, the case of "G5" to "G2" is regarded as acceptable.

-Evaluation criteria-
G1: The paper on which the image part is fixed is peeled off, and the image is severely damaged.

G2: There are slight white spots in the image defect in some parts of the image, but it is an acceptable level.

G3: Although image roughness and gloss reduction occur on each other's image surface, there is almost no image loss as an image and there is no problem.

G4: When peeling off the overlaid prints, there is a crisp sound and slight image transition is seen, but there is no image loss and there is no problem at all.

G5: No image loss or image migration is seen.

(Evaluation of environmental difference in charge amount)
Using the copying machine "bizhub PRESS (registered trademark) C1070" (manufactured by Konica Minolta), the prepared toner and developer are sequentially loaded, and the environment is low temperature and low humidity (10 ° C., 20% RH), high temperature and high humidity (30). 10,000 sheets of character images with a printing rate of 5% were printed in an environment of ° C. and 80% RH).

The developer was collected at the initial stage and after printing 10,000 sheets, and the toner charge amount was measured. The charge amount was measured using a blow-off type charge amount measuring machine "TB-200" (manufactured by Toshiba Chemical Corporation).

-Criteria-
The difference between the initial charge amount in the low temperature and low humidity environment and the high temperature and high humidity environment and the maximum value and the minimum value in the charge amount after printing 10,000 sheets was evaluated as the fluctuation range Δ.

The judgment criteria were as follows, and less than 15 μC / g was regarded as acceptable.

⊚: 0 μC / g or more and less than 10 μC / g,
◯: 10 μC / g or more and less than 15 μC / g,
X: 15 μC / g or more and less than 21 μC / g,
XX: 21 μC / g or more.

Claims (8)

To obtain a crystalline polyester resin by a polycondensation reaction between a polyvalent carboxylic acid containing an aromatic polyvalent carboxylic acid monomer and a polyhydric alcohol,
To obtain an amorphous resin by polymerizing using a monomer component containing an aromatic compound monomer,
The containing, comprising said crystalline polyester resin and the amorphous resin, a method for producing a toner for developing an electrostatic latent image,
The content of the aromatic polyvalent carboxylic acid monomer is 30 to 80 mol% with respect to the content of the polyvalent carboxylic acid.
A production method in which the content of the aromatic compound monomer is 50 to 70 mol% with respect to the content of the monomer component. The production method according to claim 1, wherein the aromatic polyvalent carboxylic acid monomer is an aromatic dicarboxylic acid having 6 to 12 carbon atoms. The aromatic polyvalent carboxylic acid monomer is phthalic acid, terephthalic acid, isophthalic acid, t-butylisophthalic acid, orthophthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-phenylene diacetic acid, diphenyl-p, p. ′ -Dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracendicarboxylic acid, 4,4'-biphenyldicarboxylic acid, trimellitic acid, pyro The production method according to claim 1, wherein the merit acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrentricarboxylic acid, or pyrenetetracarboxylic acid. The production method according to any one of claims 1 to 3, wherein the content of the aromatic polyvalent carboxylic acid monomer is 40 to 70 mol% with respect to the content of the polyvalent carboxylic acid monomer. The aromatic compound monomer is phthalic acid, terephthalic acid, isophthalic acid, t-butylisophthalic acid, orthophthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-phenylene diacetic acid, diphenyl-p, p'-dicarboxylic acid. Acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracendicarboxylic acid, 4,4'-biphenyldicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, pyrene-tricarboxylic acid, pyrene-tetracarboxylic acid, ethylene oxide adduct of bisphenol a, propylene oxide adduct of bisphenol a, f hexa methylol melamine, hexa ethylene melamine, tetramethylol benzoguanamine, tetraethyl The production method according to any one of claims 1 to 4, which is a roll benzoguanamine, a styrene monomer, or a phenyl methacrylate. The production method according to any one of claims 1 to 5, wherein the mass ratio of the amorphous resin to the crystalline polyester resin is 4 to 19. The production method according to any one of claims 1 to 6, wherein the amorphous resin contains a polyester resin. The production method according to any one of claims 1 to 7, wherein the amorphous resin contains a vinyl resin.